U.S. Pat. No. 4,000,187 disclosed a polymeric composition consisting of recurring, substituted quinoline groups, as well as methods of preparing such polymers. U.S. Pat. No. 4,000,187 is incorporated herein by this reference. As is described in the patent, polyquinoline homopolymers can be prepared from the reaction of (a) a type AA compound, an aromatic amino carbonyl containing two sets of ortho-amino carbonyl functions attached to an aromatic nucleus, selected from the group of type AA compounds consisting of structures represented by the formulas: ##STR1## wherein R is hydrogen or aryl, and the Ar, Ar', and Ar" are aryl groups, with (b) a type BB compound, a bis methylene ketone compound, selected from the group of type BB compounds consisting of the structures represented by the formulas: ##STR2## wherein R is hydrogen or aryl, R' is aryl, and Ar" and Ar"' are aryl groups.
Subsequently, it has been reported in the literature (J. K. Stille, Macromolecules, 1981, 14, 870-880) that related polyquinoline polymers can be prepared from the reaction of a compound selected from the group of type AB compounds consisting of aromatic compounds containing one set of ortho-amino carbonyl functions, as well as one methylene ketone function attached to an aromatic nucleus, selected from the group of type AB compounds consisting of structures represented by the formulas: ##STR3## wherein R is hydrogen or aryl, R' is Aryl, and Ar', Ar" and Ar"" are aryl groups.
The methods disclosed in U.S. Pat. No. 4,000,187, and in the above-described literature reference, relate to preparation of a variety of polyquinoline polymers with varying physical properties. Most of the aforementioned polymers are homopolymers; i.e., most are polymers containing regularly recurring monomer units which can be represented schematically as: ##STR4## wherein D represents a recurring monomer unit. In such polymers, the monomer units usually consist of at least one quinoline moiety, with or without substituents, connected to two identical, adjacent, monomer units. Most of the homopolymers are prepared by allowing a single type AA compound to react with an equimolar amount of a single type BB compound, or alternatively, are from the reaction of a single type AB compound.
Some of the polyquinoline homopolymers previously disclosed or reported in the literature are rigid-rod polyquinoline polymers. Rigid-rod polymers are defined as having a rigid-rod backbone formed from a plurality of monomer units joined together by parallel, covalent bonds, such as carbon-carbon covalent bonds, such that the longitudinal axis of all the covalent bonds between the monomer units is substantially parallel, resulting in a polymer backbone that is linear and substantially straight. Rigid-rod polyquinolines consist of quinoline units, with or without substituents, connected in an extended polymer chain through covalent bonds, such as in the following catenations: ##STR5## wherein X and Y represent direct covalent bonds to adjacent quinoline units, or X and Y may be any groups which permit a substantially linear linkage to adjacent quinoline groups. For example, X and Y may be 1,4-phenylene or 4,4'-biphenyl. All polyquinoline homopolymers which are not included in the class of rigid-rod polyquinoline homopolymers are referred to as non-rigid-rod polyquinoline homopolymers.
The particular type AA, type BB, and type AB compounds employed as starting materials for the preparation of any particular polyquinoline homopolymer determines whether the resulting polymer is a rigid-rod polyquinoline homopolymer or a non-rigid-rod polyquinoline homopolymer. Thus, precursors to polyquinoline polymers are divided between compounds which can be precursors for rigid-rod polyquinoline homopolymers, or compounds which cannot be precursors for rigid-rod polyquinoline homopolymers A compound which can be a precursor for a rigid-rod polyquinoline homopolymer is referred to as a "rigid-rod precursor compound," i.e., a rigid-rod type AA compound, a rigid-rod type BB compound, or a rigid-rod type AB compound. Similarly, a compound which cannot be a precursor for a rigid-rod polyquinoline homopolymer is referred to as a "non-rigid-rod precursor compound," i.e., a non-rigid-rod type AA compound, a non-rigid-rod type BB compound, or a non-rigid-rod type AB compound. It should be noted that certain specific combinations of rigid-rod precursor compounds result in the production of non-rigid-rod polyquinoline homopolymers, e.g.: ##STR6## where the substituent Ph is defined herein as a phenyl group (C.sub.6 H.sub.5).
According to U.S. Pat. No. 4,000,187, rigid-rod polyquinoline homopolymers can be prepared only by allowing a single, rigid-rod type AA compound to react with an equimolar amount of a single, rigid-rod type BB compound. Any other combination of type AA and type BB compounds in which at least one of the compounds is a non-rigid-rod compound results in formation of a non-rigid-rod polyquinoline homopolymer. In a similar fashion, use of a rigid-rod type AB compound results in a rigid-rod polyquinoline homopolymer, while use of a non-rigid-rod type AB compound yields a non-rigid-rod polyquinoline homopolymer.
A variety of both rigid-rod and non-rigid-rod polyquinoline homopolymers can be prepared according to the methods disclosed in both U.S. Pat. No. 4,000,187 and the above-described literature reference. Such homopolymers exhibit a wide range of physical properties. The contrast between rigid-rod polyquinoline homopolymers and non-rigid-rod polyquinoline homopolymers is especially notable. Most rigid-rod polyquinoline polymers are soluble only in strong acid solvents, exhibit remarkably high melting and decomposition temperatures and cannot be melt processed. In contrast, some non-rigid-rod polyquinoline homopolymers are soluble in common organic solvents, exhibit glass transition temperatures which are notably lower than for rigid-rod polyquinoline homopolymers, and can be melt processed into fibers, etc.
The number of different polyquinoline polymers which can be attained is limited by the number of type AA, type BB, and type AB compounds. Furthermore, the range of physical properties attainable with polyquinoline homopolymers is limited by the number of homopolymers which can be prepared. For example, rigid-rod polyquinoline homopolymers are expected to be especially useful in applications necessitating superior mechanical strength. However, the utility of rigid-rod polyquinoline homopolymers may be greatly limited by the difficulty in processing such materials: no rigid-rod polyquinoline homopolymers are known which can be processed from common organic solvents or which can be melt processed.
It is desirable, therefore, to provide (1) polyquinoline polymers other than homopolymers which can be utilized to prepare high quality, high temperature resistant molding and laminating resins, adhesive compositions, films, and fibers; (2) polyquinoline polymers which exhibit chemical and physical properties not attainable with polyquinoline homopolymers; (3) methods for preparing copolymers of polyquinoline polymers; (4) methods for preparing multi-block polyquinoline copolymers; (5) methods for preparing tri-block polyquinoline copolymers; (6) and methods for preparing mixtures of polyquinoline polymers.